Acrylonitrile polymer composition stabilized with formaldehyde, ethylacetoacetate, and an inorganic acid, and method of making same



United States Patent() ACRYLONTRILE POLYMER COMPOSITION STA- BILIZED WITH FRMALDEHYDE, ETHYLACE- TOA'CETATE, AND AN INORGANIC ACID,` AND METHOD OF MAKENG SAME Richard R. Holmes, Bethesda, Md., and Lloyd T. Jenkins,

Decatur, Alfa., assignors to The Chemstrand Corpora-` tion, Decatur, Alla., a corporation of Delaware No Drawing. Application May 23, 1956 Serial No. 586,665

17 Claims; (Cl. Zoll-32.6)

This. invention relates to the stabilization of acrylonitrile polymers and blends thereof.

of acrylonitrile` are generally insoluble in` the` more come monsolvents. ln those instances where suitable solvents have been found, in order tot effect solution, the application of heat is usually necessary. Where heat is employed to eifect solutions, from which shaped articles are to be formed, a tan` to` dark brown color frequently develops in the solutions and therefore is carried over into the product formed therefrom. This color also develops in solutions upon standing for prolonged periods of time.

The mechanism which causes color formation has not been' denitely ascertained, although a variety of reasons therefor have been advanced. The presenceV of metal ions, such as iron, copper and manganese in the solutions may cause the color. rThe employment of amide compounds as solvents may result in formation of amines when heat is applied and cause color in the compositions. Impurities present in the solvents have` also been cited as a cause. Whatever may be the reason for color forma-` tion, it results` in compositions and products of undesirable standards and therefore, has been the source of concern, particularly in commercial operations where such types of polymers or copolymers are employed.

Accordingly, it is an object` of the present invention to prevent undesirable color formation in acrylonitrile polymer compositions. y

Another object is to minimize color formation when solutions of the acrylonit'rile polymers are permitted to` stand for a prolonged period of time or upon of heat.

lt is also an object of the invention to prevent color application formation in acrylonitrile polymers at elevated tempera-` hyde, ethylacetoacetate and an inorganic acid having `an y y ionization constant greater than 1x10-'4.

More particularly', it relates to` the stabilization of acrylonitrile polymers The; components of the inhibiting agent may be employed in equal or unequal amounts, any one constituent being present in a range of from 98 to l percent inl a three component system. The total amount of inhibiting agent `may be employed in a range of about 0.3 to l5 percent, based on the total polymer weight. However, it is preferred that the inhibiting agent of the instant invention be present in a small amount compared to the amount of polymer dissolved. Thus, although the amount is not critical, it is preferred that the inhibiting agent be present in the amount of about 0.3 to 3 percent, based on the total weight of the polymer. The inhibiting agent may be added to the solvents before or after the polymer is dissolved therein. The inhibiting agent permits exposure to high temperatures for prolonged standing periods without the developmentv of the objectionable color which usually results in such solutions. The. compositions of the instant invention may be prepared in a varying temperature range. For example, the compositions of the instant invention may be prepared by mixing the polymer, a suitable solvent and the inhibiting agent at any temperature or heating the mixture to a temperature up to the boiling point of the solvent.

Among the acids which may be employed in practising the instant invention are sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, etc.

Among the solvents which may be used in practising the instant invention are N,N`dimethylformamide, N,N dimethylacetamide, aqueous zinc chloride, sulfuric acid, aqueous nitric acid, aqueous sodium thiocyanate, ethylene` carbonate, sulfolane, nitrornethane, etc.

`The polymeric materials, which may be employed in the practice of the present invention, are polyacrylonitrile,

copolymers including binary and ternary polymers con-` taining at least 8O percent by weight of acrylonitrile in the polymer molecule, or a blend comprising polyacrylonitrile` or copolymers comprising acrylonitrile with from 2 to 50 percent of another polymeric material, the blend having an overall polymerized acrylonitrile content of at least 8() percent by Weight. While the preferred polymers employed in the instant invention are those containing at least 80 percent of acrylonitrile,` generally recognized as the fiber-forming acrylonitrile polymers, it will be understood that the invention is likewise applicable to polymers containing less than 80 percent acrylonitrile` and the same stability is realized with` the inhibit-y ing agents defined herein. The acrylonitrile polymers contaning less than 8() percent acrylonitrile are useful in forming films, coating compositions, molding operations, lacquers, etc., in all of` which applications the alleviation of undesirable color is extremely` important.

For example, the polymer may be a copolymer of from 80l to` 98 percent acrylonitrile and from 2 to 2O percent of another monomer containing the C=C linkage and copolymerizable with acrylonitrile.` Suitable monoolelinic monomers include acrylic, alphachloroacrylic and` methacrylic acids; the acrylates, such as methylmethlacrylate, ethylmethacrylate, butylmethacrylate, methoxymethyl methacrylate, beta-chloroethylmethacrylate, and thecorresponding esters oflacrylic and alpha-chloroacrylic acids; vinyl chloride, vinyl lluoride, vinyl bromide, vinyli` dene chloride, l-chlbro-l-bromoethyleneg methacrylonitrile; acrylamide and methacrylamide; alpha-chloroacrylamide,` or monoalkyl substitution products thereof; methyl vinyl ketone; vinyl carboxylates, such as vinyl i y acetate, vinyl chloroacetate, vinyl propionate, andvinyl stearato; N-vinyiirnides, such as Il-vinylphthalimide` and Nsvinylsuccinimide; methylene malonic esters; itaconic acid and itaconic ester; N-vinylcarbazole; vinyl furane; alkyl vinyl esters; `vinyl `sulfonic acidyethyliene alpha;

beta-dicarboxylic acids ortheir anhyclrides` or derivatives,

'assent o such asr diethyleitraconate, diethylm'esaconate, styrene,

acrylonitrile and two or more of any of the monomers, n

other than acrylonitrile, enumerated above. More specically, and preferably', the ternary polymer comprises acrylonitrile, methacrylonitrile, and 2-vinylpyridine. The ternary polymers preferably contain from 8O to 97 percent of acrylonitrile, from l to l percent of a vinylpyridine or a` l-vinylimidazole, and from 1 to 18 percent of another substance, such as methacrylonitrile or vinyl chloride.

The polymer may also be a blend of polyacrylonitrile orof a binary interpolymer of from 80 to 99 percent acrylonitrile and from 1 to 20 percent of at least one other ChC containing substance with from 2 to 50 percent of the weight of the blend of a copolymer of from to 70 percent of acrylonitrile and from 30 to 90 percent of at least one other C2==C containing polymerizable monomer. Preferably, when the polymeric material comprises a blend, it `will be a blend of a copolymer of 90A to 98 percent acrylonitrile and from 2 to 10 percent of another mono-olelinic monomer, such as vinyl acetate, which is not receptive to dyestutf with, a sufficient amount of a copolymer of from 10 to 70 percent of acrylonitrile and from 30 to 90 percent of a vinyl-substituted tertiary heterocyclic amine, such as vinylpyridine or l-vinylimidazole, to give a dyeable blend having an overall vinyl-substituted tertiary heterocyclc amine content of from 2 to 10 percent, based on the -weight of the blend.

The polymers, useful in the practice of the present invention, may be prepared by any conventional polymerization procedures, such as mass polymerization methods, solution polymerization methods, or aqueous emulsion procedures. However, the preferred practice utilizes suspension polymerization wherein the polymer is prepared in finely divided form for immediate use in the ber fabrication operations. The preferred suspension polymerization may utilize batch procedures, wherein monomers are charged with an aqueous medium containing the necessary catalyst and dispersing agents. A more desirable method involves the semi-continuous procedure in which the polymerization reactor containing the aqueous medium is charged with the desired monomers and the continuous withdrawal of polymer may also be employed.

The polymerization is catalyzed by means of any water-soluble peroxy compound, for example the potassium, ammonium and other water-soluble salts of peroxy acids, sodium peroxide, hydrogen peroxide, sodium perborate, the sodium salts of other peroxy acids, and any other water-soluble compound containing a peroxy group (-O-O-) A wide variation in the quantity of peroxy compound is possible. For example, from 0.1 to 3.0 percent by weight of the polymerizable monomer may be used. The catalyst may be charged at the outset of the reaction, or it may be added continuously or in increments throughout the reaction for the purpose of maintaining a more uniform concentration of catalyst in the reaction mass. The latter method is preferred because it tends to make the resultant polymer more uniform in its chemical and physical properties.

Although the uniform distribution of the reactants throughout the reaction mass can be achieved by vigorous agitaation, it is generally desirable to promote the 4 agents, or emulsion stabilizers. Suitable reagents for this purpose are the water-soluble salts of fatty acids, such as sodium oleate and potassium stearato, mixtures of water-soluble fatty acid salts, such as common soaps prepared by the saponification of animal and vegetable oils, the amino soaps, such as salts of triethanolatnine and dodecylmethylamine, salts of rosin acids and mixtures thereof, the water-soluble salts of half esters of sulfuric acid and long chain aliphatic alcohols, sulfonated hydrocarbons, such as alkyl aryl sulfonates, and any other of a wide variety of wetting agents, which are in general organic compounds containing both hydrophobic and hydrophilic radicals. The quantity of emulsifying agents will depend upon the particular agents selected, the ratio of monomer to be used, and the conditions of polymerization. In general, however, from 0.01 to 1.0 percent by weight of the monomers may be employed.

The emulsion polymerizations are preferably conducted in glass or glass-lined vessels which are provided with ameans for agitating the contents. Generally rotary stirring 'devices are the most effective means of insuring the intimate contact of the reagents, but other methods may be successfully employed, for example by rocking or tumbling the reactors. The polymerization equipment generally used is conventional in the art and the adaptation of a particular type of apparatus to the reaction contemplated is within the province of one skilled in the art. The articles manufactured therefrom may be produced by well-known conventional methods, for example, the wet-spinning, dry-spinning and melt-spinning methods for producing fibers.

The following examples are illustrative rather than limitative and all parts, proportions and percentages are by weight unless otherwise specified.

EXAMPLE I 7.5 grams of a polymer blend of 88 percent of a copolymer containing 94 percent of acrylonitrile and 6 percent of vinyl acetate and 12 percent of a copolymer of 50 percent of acrylonitrile and 50 percent of Z-methyl- S-vinyl pyridine were added to 45 milliliters of N, N- dimethylacetamide containing approximately 0.05 gram of titanium dioxide. The mixture was stirred and heated to 70 C. It was then quickly cooled to room temperature and the color measured. This sample was used as a control. The purity is set forth below. Subsequently, a like sample was prepared but with 0.225 gram of a color inhibitor containing 0.075 gram each of formaldehyde, ethylacetoacetate and ysulfuric acid. The purity is set forth below.

Table l Percentage Purity Used EXAMPLE II :animato Inhibitor ,ieroentageA Purity Used contini-y l 10.2 Formaldehyde, Ethylacetoacetate and Sulfurie ci i 3 7.5

X" LA MPLE IIIV Table III Inhibitor Percentage Purity Used Control- 8.5 Formaldehyde, Ethylacetoacetate and Suliuric Acid .r 3 5. 2

The tests for color indicative of approaching whiteness used throughout the examples consist of measurements of purity as calculated from the tristimulus values deltermined on a General Electric spectrophotometer by the methods recommended by the Standard Observer and Coordinate System of the International Commission on Illumination, as fully set forth in the Handbook of Colorimetry published by The Technology Press, Massachusetts Institute of Technology in 1936.

The compositions of the instant invention present many advantages. For example, products formed from the polymer solutions of the instant invention are free of objectionable color and therefore of greater commercial value. In preparing the polymer solutions, heat may be applied without the danger of color formation and the solutions, if necessary, may stand for prolonged periods and remain free of color. The inhibiting agents are readily available and inexpensive. Therefore, no great increase in production cost is necessary. The compositions containing the inhibitors may be prepared without going through detailed and elaborate procedures that necessitate expensive changes in the design of the apparatus used to manufacture them.

It will be understood to those skilled in the art that many apparently widely different embodiments of this invention can be made without departing from the spirit and scope thereof. Accordingly, it is to be understood that this invention is not to be limited to the specific embodiments thereof except as dencd in the appended claims.

We claim:

1. A new composition of matter comprising a polymer containing at least 80 percent of polymerized acrylonitrile and up to 20 percent of another polymerizable mono-olefinic monomer copolymerizable therewith, a solvent therefor, and an inhibiting agent containing substantially equal proportions by weight of formaldehyde, ethylacetoacetate and an inorganic acid having an ionization constant greater than 1x10-4.

2. A new composition of matter as defined in claim 1 wherein the polymer is a copolymer containing from 80 to 98 percent of acrylonitrile and from 2 to 2O percent of another polymerizable mono-olenic monomer copolymerizable therewith.

3. A new composition of matter as dened in claim 1 (A) a copolymer containing 90 tc`r98Y percent of acrylonitrile and 2 to 10 percent of vinyl* acetate andl to 20 percent `of `(B) a` copolymer containing 10 to' 70 percent of acrylonitrile and 30 to 90 percent of 2-methyl-5-v`inyl pyridine. l

4. A new composition of matter as dened in claim 1 wherein the polymer is polyacrylonitril.

5. A new composition of matter as defined in claim` 1 wherein the solvent is N,N-dimethylformaldehyde.

6. A new composition of matter as defined in claim 1 wherein the solvent is N,N-dimethylacetamide.

7. A new composition of matter comprising a polymer blend of (A) a` copolymer containing 90 to 983 percent of acrylonitrile and 2 to 10 percent of another polymerizable mono-olenic monomer anid (B) a copolymer containing 10" to 70 percent of acrylonitrile and 30 to 90 percent of a vinyl substituted tertiary heterocycylic amine, said blend having an overall vinyl substituted tertiary heterocyclic amine content of from 2 to 10 percent based on the weight of the blend, a solvent therefor, and an inhibiting agent containing substantially equal proportions by weight of formaldehyde, ethylacetoacetate and an inorganic acid having an ionization constant greater than 1x10-4.

8. A new composition of matter comprising a copolymer containing to 98 percent of acrylonitrile and 2 to 20 percent of vinyl acetate, a solvent therefor, and 0.3 to 15 percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of formaldehyde, ethylacetoacetate and sulfuric acid..

9. A new composition of matter comprising a polymer blend of 80 to 99 percent of (A) a copolymer containing to 98 percent of acrylonitrile and 2 to 10 percent of vinyl acetate and 1 to 20 percent of (B) a copolymer containing l0 to 70 percent of acrylonitrile and 30 to` 90 percent of 2-methyl-5-vinyl pyridine, a solvent therefor, and 0.3 to 15 percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of formaldehyde, ethylacetoacetate and sulfuric acid.

10. A new composition of matter comprising a polymer containing at least 80 percent of polymerized acrylonitrile and up to 20 percent of another polymerizable mono-olenic monomer copolymerizable therewith, a solvent therefor, and 0.3 to 15 percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of formaldehyde, ethylacetoacetate and sulfurie acid.

11. A new composition of matter comprising polyacrylonitrile, a solvent therefor, and 0.3 to l5 percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of formaldehyde, ethylacetoacetate and sulfuric acid.

12. A method for preparing a new composition of matter comprising mixing a polymer containing at least 80 percent of polymerized acrylonitrile and up to 20 percent of another polymerizable mono-olefnic monomer copolymerizable therewith, a solvent therefor, and an inhibiting agent containing substantially equal proportions by weight of formaldehyde, ethylacetoacetate and an inorganic acid having an ionization constant greater than 1X 104; and heating the mixture to form a homogeneous solution.

13. The method as defined in claim 12 wherein the polymer is a copolymer containing from 80 to 98 percent of acrylonitrile and from 2 to 20 percent of another polymerizable mono-oleiiuic monomer copolymerizable therewith.

14. The method as defined in claim 12 wherein the polymer is a blend of 80 to 99 percent of (A) a copolygamma,

nier containing 90\to-98- percent of acrylonitrleand 2 to I10 percent of vinyl acetate and 1 to 2O percent of (B) a copolymer containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of 2-mcthyl-5-vinyl pyridine.

1S. The method as dened in claim 12 wherein the polymer is polyacrylonitrle.

16. A method for preparing a new composition of matter comprising mixing a copolymer containing 80 to 98 percent of acrylonitrile and 2 to 20 percent of vinyl acetate, a solvent therefor, and 0.3 to 15 percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by Weight of formaldehyde, ethylacetoacetate and sulfuric acid, and heating the mixture to a temperature in a range of 25 C. to the boiling point of the mixture to form a homogeneous solution.

17. A method for preparing a new composition of matvinylpyridine, a solvent therefor, a nd 0.3 to 15 percent,`

based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of formaldehyde, ethylacetoace-l tate and sulfuric acid, and heating the mixture to a temperature in a range of 25 C. to the boiling point of the mixture to form a homogeneous solution.

References Cited in the le of this patent UNITED STATES PATENTS y2,502,030 scheiderbauer Mar. 2s, 195o UNTTTn STATES PATENT OFFICE @ETIHCATE 0F CORRECTION Patent Noo 878,216 Mayen l?, 1959 Rehard R, Holmes et al,

It is hereby certified that error appears in theprnted specification of the above numbered patent requiring correction and that the said Letters Patent should` read as corrected below.

Signed and sealed, this 28th day of July 1959,

(SEAL) Attest:

KARL XlLlNE ROBERT C. WATSON Commissioner of Patents Attesting Officer 

1. A NEW COMPOSITION OF MATTER COMPRISING A POLYMER CONTAINING AT LEAST 80 PERCENT OF POLYMERIZED ACRYLONITRILE AND UP TO 20 PERCENT OF ANOTHER POLYMERIZABLE MONO-OLEFINIC MONOMER COPOLYMERIZABLE THEREWITH, A SOLVENT THEREFOR, AND AN INHIBITING AGENT CONTAINING SUBSTANTIALLY EQUAL PROPORTIONS BY WEIGHT OF FORMALDEHYDE, ETHYLACETOACETATE AND AN INORGANIC ACID HAVING AN IONIZATION CONSTANT GREATER THAN 1X10-4. 